The reaction of an olefin with hydrogen and carbon monoxide to produce alcohols is the well known hydroformylation/reduction reaction also known as the oxo reaction. One art-recognized oxo method of preparing alcohols from olefins is a two-step process wherein the first step is contacting at elevated temperature and pressure an olefin with a synthesis gas mixture of hydrogen and carbon monoxide in the presence of an oxo catalyst to produce a mixture of aldehydes; then, in the second step, these aldehydes are hydrogenated to their corresponding alcohols. A one-step oxo process for the production of alcohols utilizes a cobalt carbonyl phosphine catalyst. Cobalt and rhodium are frequently used as the oxo catalysts. The classical oxo catalyst precursor is octocarbonyldicobalt, Co.sub.2 (CO).sub.8, formed by reaction of metallic cobalt with carbon monoxide. The complex RhH(CO)(Ph.sub.3 P).sub.3 is even more efficient than the cobalt complex at promoting the oxo reaction.
The oxo process was discovered in Germany during World War II, and was the first industrial application of catalysis by a transition metal complex. When using homogeneous catalysis with transition metal complex catalysts that are soluble in the liquid reaction mixture during the hydroformylation/reduction reaction, there is a recovery and regeneration step necessary for cost reduction for the dissolved transition metal catalyst due to the expense of the metal itself and the need to minimize loss. Even with sophisticated recovery methods, small losses of metal will occur, thus the economic use of homogeneous catalysis using a transition metal complex catalyst is limited.
Heterogeneous catalysis can be done in the oxo reaction using a catalyst containing a transition metal complex supported upon solid polymers or resins. However, the problem with metal leaching from the solid-supported catalyst is still a major consideration due to the high cost of recovery or replacement of the transition metal catalyst. This metal leaching occurs because some species in the oxo process is a better ligand, forming a stronger bond with the metal complex than the ligand functionality of the solid support. Garrou et al, U.S. Pat. No. 4,262,147 and Hartwell et al, U.S. Pat. No. 4,144,191 discuss catalysts of transition metal complexes supported by amine resins. Haag et al, U.S. Pat. No. 4,098,727 teaches use of a polymer as a solid support for transition metal complexes which then are less soluble in the liquid reaction mixture due to strong chemical bonds between the polymer and the metal complex. In the Haag et al patent, polystyrene resins with tertiary amine functional groups serve as a solid support for a rhodium catalyst prepared using RhCl.sub.3.XH.sub.2 O.
The inventive concept of this disclosure is the unexpected recognition that halogens, specifically chlorine, poison or inhibit the hydroformylation/reduction reaction of olefins to alcohols using a rhodium catalyst on a tertiary amine resin. As a result of this invention, a combined hydroformylation/reduction reaction is enhanced because catalyst reactivity is greater and catalyst life is longer. That halogens are a poison was not expected since U.S. Pat. No. 4,098,727 teaches using RhCl.sub.3 XH.sub.2 O to prepare a rhodium catalyst containing 2.23% chlorine.